Fullerene based proton conductive materials

Abstract

A fullerene-based proton conductor including a proton conductive functional group connected to the fullerene by an at least partially fluorinated spacer molecule. Also, a polymer including at least two of the proton conductors that are connected by a linking molecule. Further, an electrochemical device employing the polymer as a proton exchange membrane, whereby the device is able to achieve a self-humidifying characteristic.

1. A proton conductor comprising a fullerene molecule, a spacer molecule attached to said fullerene molecule, and a proton conductive functional group attached to said spacer molecule wherein said spacer molecule is an at least partially fluorinated molecule. 
     
     
       2. The proton conductor of  claim 1 , wherein said fullerene molecule is selected from the group consisting of C 60 , C 70  and combinations thereof. 
     
     
       3. The proton conductor of  claim 1 , wherein said spacer molecule comprises an at least partially fluorinated hydrocarbon molecule. 
     
     
       4. The proton conductor of  claim 3 , wherein said spacer molecule is selected from the group consisting of a partially fluorinated compound, a perfluorinated compound, and combination thereof. 
     
     
       5. The proton conductor of  claim 4 , wherein said perfluorinated compound comprises the general formula C n F 2n , where n is a natural number. 
     
     
       6. The proton conductor of  claim 4 , wherein said perfluorinated compound includes CF 2 —CF 2 —O—CF 2 —CF 2 . 
     
     
       7. The proton conductor of  claim 4 , wherein said perfluorinated chain includes CF 2 . 
     
     
       8. The proton conductor of  claim 1 , further comprising a plurality of said spacer molecules attached to said fullerene. 
     
     
       9. The proton conductor of  claim 8 , further comprising a proton conductive functional group attached to each of said spacer molecules. 
     
     
       10. The proton conductor of  claim 9 , wherein at least one of said proton conductive functional groups is an acidic functional group. 
     
     
       11. The proton conductor of  claim 9 , wherein at least one of said proton conductive functional groups is selected from the group consisting of a sulfuric acid ester, a sulfonic acid, a phosphoric acid ester, a carboxylic acid and combinations thereof. 
     
     
       12. The proton conductor of  claim 1 , wherein said proton conductive functional group is an acidic functional group. 
     
     
       13. The proton conductor of  claim 12 , wherein said proton conductive functional group is selected from the group consisting of a sulfuric acid ester, a sulfonic acid, a phosphoric acid ester, and a carboxylic acid and combinations thereof. 
     
     
       14. A method of making a proton conductor comprising:
 combining a fullerene with a spacer-molecule precursor wherein said spacer-molecule precursor comprises an at least partially fluorinated compound and includes an acid precursor group forming a first reaction product;  
 hydrolyzing the first reaction product;  
 forming a second reaction product;  
 protonating the second reaction product; and  
 forming a proton conductor including a proton conductive functional group attached to said fullerene by a spacer molecule that is formed from said spacer-molecule precursor and that is at least partially fluorinated.  
 
     
     
       15. The method of making a proton conductor according to  claim 14 , wherein said fullerene is C 60  and said spacer-molecule precursor is I—CF 2 —CF 2 —O—CF 2 —CF 2 —SO 2 F, wherein said first reaction product is C 60 —(CF 2 —CF 2 —O—CF 2 —CF 2 —SO 2 F) n . 
     
     
       16. The method of making a proton conductor according to  claim 15 , wherein forming the first reaction product is carried out with one equivalent amount of C 60  and twenty-four equivalent amounts of I—CF 2 —CF 2 —O—CF 2 —CF 2 —SO 2 F in a solution of 1:1 C 6 F 6 /CS 2  at a temperature of about 200° C. for about 94 hours so as to form a plurality of said first reaction products each having the general formula C 60 —(CF 2 —CF 2 —O—CF 2 —CF 2 —SO 2 F) n , where n is a natural number up to about 8. 
     
     
       17. The method of making a proton conductor according to  claim 15 , wherein forming said second reaction product includes combining said first reaction products with a sufficient amount of C 6 F 6  to form a solution, adding from about 10 volume equivalents to about 20 volume equivalents of THF, and adding C 6 F 6 +THF of 1 mol/liter of NaOH per one equivalent of C 60  used in forming the first reaction product so as to produce a plurality of said second reaction products having the general formula C 60 —(CF 2 —CF 2 —O—CF 2 —CF 2 —SO 3 Na) n , where n is a natural number. 
     
     
       18. The method of making a proton conductor according to  claim 17 , further comprising the step subsequent to forming the second reaction product of removing an amount of excess NaOH by passing the solution through a silica gel column having THF and water in a 1:1 ratio; and then removing the THF and water. 
     
     
       19. The method of making a proton conductor according to  claim 18 , wherein the step of forming the proton conductor includes forming a solution of the second reaction products and water, and then passing said solution through an ion exchange column, so as to produce a plurality of said third reaction products having the general formula C 60 —(CF 2 —CF 2 —O—CF 2 —CF 2 —SO 3 H) n , where n is a natural number.